EP0722919A1 - Keramischer Verbundkörper - Google Patents

Keramischer Verbundkörper Download PDF

Info

Publication number
EP0722919A1
EP0722919A1 EP96100600A EP96100600A EP0722919A1 EP 0722919 A1 EP0722919 A1 EP 0722919A1 EP 96100600 A EP96100600 A EP 96100600A EP 96100600 A EP96100600 A EP 96100600A EP 0722919 A1 EP0722919 A1 EP 0722919A1
Authority
EP
European Patent Office
Prior art keywords
ceramic composite
oxides
oxide
phase
solidified body
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96100600A
Other languages
English (en)
French (fr)
Other versions
EP0722919B1 (de
Inventor
Yoshiharu Waku
Narihito Nakagawa
Hideki Ohtsubo
Takumi Wakamoto
Kazutoshi Shimizu
Yasuhiko Kohtoku
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ube Corp
Original Assignee
Ube Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ube Industries Ltd filed Critical Ube Industries Ltd
Publication of EP0722919A1 publication Critical patent/EP0722919A1/de
Application granted granted Critical
Publication of EP0722919B1 publication Critical patent/EP0722919B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/111—Fine ceramics
    • C04B35/117—Composites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/111—Fine ceramics
    • C04B35/117—Composites
    • C04B35/119—Composites with zirconium oxide

Definitions

  • the present invention relates to a ceramic composite which has a high mechanical strength, and an excellent creep resistance in a wide temperature range from room temperature to a high temperature and is suitable for use as a structural material at a high temperature.
  • SiC and Si 3 N 4 have been investigated to develop ceramic materials to be used at high temperatures but they are not sufficient in high temperature properties.
  • the temperature range at which they can be used is reported to be 1400°C or lower.
  • Manufacture of ceramics is primarily done by a powder sintering method in which improvement in powder characteristics, such as finer particle size and higher purity, have made it possible to obtain ZrO 2 ceramics having the high strength, at room temperature, of 30 GPa. It is also possible to produce a composite material in which additional ceramic particles are dispersed at the level of nano meters in a sintered ceramic material, by which an improvement in the strength, toughness and thermal properties of the ceramic material was provided.
  • oxide ceramics cannot be used for high temperature structural materials which receive high loads, since oxide ceramics are easily deformed at high temperatures.
  • the oxide ceramics are better in resistance to oxidation and corrosion at high temperatures than other types of ceramics and therefore can be expected to be used in a wide range of uses if the mechanical strength at high temperature can be enhanced.
  • metal oxides such as Al 2 O 3 , ZrO 2 and MgO and rare earth element oxides such as Y 2 O 3 , La 2 O 3 , Yb 2 O 3 , Sm 2 O 3 , Gd 2 O 3 , Nd 2 O 3 and Er 2 O 3 , having melting points higher than 2000°C, are expected to be useful for high temperature ceramics.
  • Japanese Unexamined Patent Publication (Kokai) No. 5-85821 discloses a sintered body comprising a rare earth element oxide (an oxide of a rare earth element or an oxide of two or more rare earth elements) and Al 2 O 3 and a process for producing the same.
  • a rare earth element oxide and Al 2 O 3 are mixed and formed into a shape, followed by sintering the shape at an optimum sintering temperature for an optimum sintering time period so as to control the crystal grain size of the sintered body to 30 ⁇ m or less, by which extraordinal grain growth and the appearance of pores are prevented and a rare earth element oxide-alumina sintered body with a high strength, high toughness and high reliability can be provided.
  • YAG yttrium aluminum garnet
  • Mr. Parthasarathy et al. also disclose a method of producing the composite by unidirectionally melting and solidifying a mixed powder of Al 2 O 3 and Y 2 O 3 in a crucible.
  • This composite material has stresses equivalent to those of sapphire at 1530°C and 1650°C when the strain rate was made constant.
  • the present inventors confirmed by experiment that the composite disclosed by Mr. Parthasarathy et al. include pores or voids in the microstructure and the mechanical strength of the composite falls rapidly at high temperature.
  • the present inventors considering the above problems of the conventional art, have vigorously investigated to obtain ceramic composite materials having excellent mechanical strength and creep resistance from room temperature to a high temperature, particularly having remarkably improved properties at high temperatures.
  • novel ceramic composite materials consisting of ⁇ -Al 2 O 3 and YAG, constituting single crystal/single crystal phases, single crystal/polycrystal phases, and polycrystal/polycrystal phases (see Japanese Unexamined Patent Publication (Kokai) Nos. 07-149,597 and 07-187893 and Japanese Patent Application No. 06-240790).
  • the object of the present invention is to provide, following the above ceramic composite materials consisting of ⁇ -Al 2 O 3 and YAG phases, novel ceramic composites of solidified bodies consisting of at least two crystal phases of oxides selected from metal oxides and complex metal oxides, i.e., metal oxide/metal oxide, metal oxide/complex metal oxide, or complex metal oxide/complex metal oxide, which have excellent mechanical properties and creep resistances at from room temperature to a high temperature and particularly, remarkably enhanced properties at high temperatures.
  • a ceramic composite of a solidified body consisting of at least two crystal phases of oxides selected from the group consisting of metal oxides and complex metal oxides, except that said at least two oxides are not the combination of aluminum oxide (Al 2 O 3 ) and a complex oxide (YAG) of aluminum oxide (Al 2 O 3 ) and yttrium oxide (Y 2 O 3 ).
  • Exemplified metal oxides include Al 2 O 3 , MgO, SiO 2 , TiO 2 , ZrO 2 , CaO, BaO, BeO, FeO, Fe 2 O 3 , MnO, CoO, Nb 2 O 3 , Ta 2 O 3 , Cr 2 O 3 , SrO, ZnO, NiO, Li 2 O 3 , Ga 2 O 3 , HfO 2 , ThO 2 , UO 2 and SnO 2 .
  • Exemplified rare earth element oxides include La 2 O 3 , Y 2 O 3 , CeO 2 , Pr 6 O 11 , Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Tb 4 O 7 , Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 and Lu 2 O 3 .
  • a complex metal oxide also called as compound oxide or sometimes double oxide, means an oxide of two or more metal elements.
  • Exemplified complex metal oxides include 3Al 2 O 3 ⁇ 2SiO 2 , MgO ⁇ Al 2 O 3 , Al 2 O 3 ⁇ TiO 2 , BaO ⁇ Al 2 O 3 , BaO ⁇ 6Al 2 O 3 , BeO ⁇ Al 2 O 3 , BeO ⁇ 3Al 2 O 3 , 3BeO ⁇ Al 2 O 3 , CaO ⁇ TiO 2 , CaO ⁇ Nb 2 O 3 , CaO ⁇ ZrO 2 , 2CoO ⁇ TiO 2 , FeAlO 4 , MnAlO 4 , 2MgO ⁇ Y 2 O 3 , 2MgO ⁇ SiO 2 , MgCr 2 O 4 , MgO ⁇ TiO 2 , MgO ⁇ Ta 2 O 5 , MnO ⁇ TiO 2 , 2MnO ⁇ TiO 2 , 3SrO ⁇ Al 2 O 3 , SrO ⁇ Al 2 O 3 , SrO ⁇
  • Exemplified complex metal oxides of Al 2 O 3 and rare earth element or metal include 11Al 2 O 3 ⁇ La 2 O 3 , 11Al 2 O 3 ⁇ Nd 2 O 3 , 11Al 2 O 3 ⁇ Pr 2 O 3 , EuAl 11 O 18 , 2Gd 2 O 3 ⁇ Al 2 O 3 , Sm 2 O 3 ⁇ 11Al 2 O 3 , Yb 3 Al 5 O 12 , CeAlO 3 , CeAl 11 O 18 , Er 3 Al 5 O 12 and Er 14 Al 2 O 9 .
  • the oxide of each crystal phase may be any of a single oxide such as Al 2 O 3 , a complex oxide such as MgO ⁇ Al 2 O 3 , or a solid solution oxide.
  • the solid solution oxide means an oxide consisting of a primary oxide to which an additional oxide is solid solved.
  • solidified body means that the body is obtained by molting the powders or materials of at least two oxides followed by cooling the molten material to allow solidification "solidified” is sometimes also called “melted” or “fused” as, for example, in “melted alumina” or “fused alumina”.
  • the solidified body is clearly distinguished from a sintered body.
  • the ceramic composite of the present invention can have a uniform structure which does not include colonies and voids by controlling the conditions of manufacture.
  • the ceramic composite of the present invention does not include any of the grain boundary phases which are generally present in sintered ceramic bodies and are constituted by a material having a composition different from each of the compositions of the crystal grains, for example, a sintering agent or a reaction product or mixture thereof.
  • a ceramic composite constituted by a combination of the crystal phases of single crystal/single crystal, single crystal/polycrystal, or polycrystal/polycrystal of a combination of metal oxide-metal oxide, metal oxide-complex metal oxide, or complex metal oxide-complex metal oxide, by controlling the conditions of manufacture.
  • the single crystal means that only a diffraction peak derived from a specific crystal plane is observed in an X-ray diffraction of a ceramic composite.
  • the ceramic composite includes only one single crystal or a plurality of single crystals which are aligned in the same crystallographic orientation, most typically a three dimensionally continuous single crystal.
  • each phase of the single crystal and polycrystal phases can have a three dimensionally continuous structure and these three dimensionally continuous phases are typically intertmingled with each other.
  • the only polycrystal phase may be a three dimentionally continuous phase in which a plurality of single crystals may be dispersed in the form of fibers or particles.
  • the sizes of phases may be controlled by selecting the solidification conditions but is typically 1 to 50 ⁇ m.
  • the size of a phase means a dimension of the phase which is observed in a section of a ceramic composite. Most typically, the sectional view takes a sea-island structure (e.g. Fig. 1).
  • a complex oxide made of Al 2 O 3 and SiO 2 can be obtained, since they form an eutectic crystal consisting of 68 mol% of Al 2 O 3 and 32 mol% of SiO 2 .
  • the proportion between Al 2 O 3 and the complex oxide 3Al 2 O 3 ⁇ 2SiO 2 can be varied in a range of about 20 to 80% by volume of Al 2 O 3 and about 80 to 20% by volume of 3Al 2 O 3 ⁇ 2SiO 2 by varying the ratio between the starting Al 2 O 3 and SiO 2 powders.
  • a ceramic composite consisting of an Al 2 O 3 phase and a GdAlO 3 phase having a perovskite structure of a complex oxide made of Al 2 O 3 and Gd 2 O 3 can be obtained.
  • This ceramic composite may have a composition in a range of about 20 to 80% by volume of ⁇ -Al 2 O 3 and about 80 to 20% by volume of GdAl 2 O 3 .
  • the oxides having a perovskite structure which can be present in accordance with the present invention include LaAlO 3 , CeAlO 3 , PrAlO 3 , NdAlO 3 , SmAlO 3 , EuAlO 3 and DyAlO 3 .
  • a ceramic composite comprising at least one oxide having a perovskite structure can have a finer structure and, as a result, an enhanced mechanical strength.
  • a ceramic composite consisting of an Al 2 O 3 phase and an Er 3 Al 5 O 12 phase having a garnet structure of a complex oxide made of Al 2 O 3 and Er 2 O 3 can be obtained.
  • the ceramic composite may comprises about 20 to 80% by volume of ⁇ -Al 2 O 3 and about 80 to 20% by volume of Er 3 Al 5 O 12 .
  • the oxides having a garnet structure which can be present in accordance with the present invention include Yb 3 Al 5 O 12 , etc.
  • a ceramic composite comprising at least one oxide having a garnet structure can have an improved creep resistance.
  • the ceramic composite of the present invention can be produced, for example, by the following process.
  • a mixed powder of at least two oxide ceramic powders in a ratio for a desired ceramic composite is prepared by weighing and mixing.
  • the mixing method is not particularly limited and may be either of a dry mixing method or a wet mixing method.
  • an alcohol such as methanol or ethanol is generally used as the medium.
  • the mixed powder is then heated to a temperature at which both starting powders are molten, for example, at 1950 to 2100°C in the case of Al 2 O 3 and SiO 2 , in a conventional furnace, for example, an arc furnace, to melt the mixed powder.
  • a conventional furnace for example, an arc furnace
  • the melt is charged in a crucible and then unidirectionally solidified to prepare a ceramic composite of the present invention.
  • the melt is once solidified and crushed and the crushed material is then charged in a crucible and melted and unidirectionally solidified.
  • the above melt is cast in a crucible heated to a predetermined temperature which is then cooled while controlling the cooling rate to obtain a solidified body.
  • the atmospheric pressure during the melting and solidification is generally 300 Torr or less, preferably 10 -3 Torr or less.
  • the speed of moving the crucible for unidirectional solidification i.e., the rate of growth of the ceramic composite material is generally 500 mm/hour or less, preferably 1 to 100 mm/hour.
  • the control of the conditions other than the atmospheric pressure and crucible moving speed can be done in the same manner as in conventional methods.
  • the apparatus for unidirectional solidification may be a conventional one in which a crucible is vertically movably mounted in a vertically arranged cylindrical container, an induction heating coil is disposed around the approximate center position of the cylindrical container, and a vacuum pump is provided to evacuate the container space.
  • the ceramic composites of the present invention are remarkably improved in their heat resistance, durability, strength, thermal stability and the like at high temperatures, exhibiting excellent characteristics at a high temperature above 1500°C in air, and therefore they are highly useful as members such as turbine blades of jet engines, electric power generator turbine, and the like as well as jigs for measuring high temperature properties.
  • oxide-based ceramics such as Al 2 O 3 are used in practice, for example, in a heat exchanger for a high temperature furnace, as materials for a neclear fusion furnace, as materials for a nuclear furnace, as abrasion resistance materials, and as corrosion resistance materials.
  • the ceramic composites are made into the form of fibers or powders, they can be suitably used as reinforcing members dispersed in ceramic composite materials or nickel-based super alloys or cobalt-based super alloys which are used in the turbine blades of power generation turbines or in jet engines. Further, the obtained powders may be melted and solidified on the surface of a metal member or others by a method such as plasma spraying, which is expected to improve the oxidation resistance and the abrasion resistance.
  • Formation of the ceramic composite in the form of fibers may be conducted, for example, by changing a solidified body obtained by unidirectional solidification into a wire having a diameter of about 1 mm, dipping an end of the thus obtained wire into a pool of a melted material having the same composition as that of the wire, and drawing the wire to grow a crystal in the form of a fiber.
  • the Edge-defined Film-fed Growth method in which a guide is placed in a melt pool to cause capillary action and the guide is drawn
  • the Laser Heated Float Zone (LHF) method in which a rod previously prepared by sintering is irradiated with a beam such as a laser beam to zone melting and unidirectional solidification, may be adopted.
  • Formation of the ceramic composite in the form of powder may be conducted by a method in which a melted material is dropped through fine pores formed at the bottom of a crucible into a furnace having a graduation of temperature so as to solidify the same.
  • the surface coating may be conducted by immersing a member to be coated into a melt pool, unidirectionally solidifying the melt while immersing the member therein, and removing the crucible which held the melt by post-machining or processing.
  • ⁇ -Al 2 O 3 powder and Gd 2 O 3 powder in a molar ratio of 78.0% by mole of the former to 22.0% by mole of the latter were milled in a wet ball mill using ethanol.
  • the obtained slurry was dried in a rotary evaporator to remove the ethanol.
  • the obtained mixed powder of ⁇ -Al 2 O 3 and Gd 2 O 3 was charged in a molibdenum crucible in a chamber, in which the atmospheric pressure was maintained at 10 -5 Torr and the crucible was heated by an induction coil to 1850 to 2000°C to melt the mixed powder in the crucible. Subsequently, unidirectional solidification was conducted by lowering the crucible, at a speed of 5 mm/hour and under the above atmospheric pressure, to obtain a unidirectionally solidified body.
  • Fig. 1 shows scanning electron micrograph of the thus obtained solidified body in a section cut perpendicular to the direction of the solidification.
  • the white portions are a GdAlO 3 phase and the black portions are an ⁇ -Al 2 O 3 phase.
  • the ceramic composite of the solidified body does not include any colony or grain boundary phase, that pores or voids do not exist, and that a uniform structure is obtained.
  • the mechanical strength of the ceramic composite is shown in Table 1, where the three point bending strength was measured in air. The ceramic composite was kept at 1750°C for 50 hours and the increase in weight was 0.003 g/cm 3 .
  • Table 1 Example 1
  • Example 2 Three point bending strength (MPa) 600 1000
  • ⁇ -Al 2 O 3 powder and Gd 2 O 3 powder in a molar ratio of 78.0% by mole of the former to 22.0% by mole of the latter were milled in a wet mill using ethanol.
  • the obtained slurry was dried in a rotary evaporator to remove the ethanol.
  • the obtained mixed powder of ⁇ -Al 2 O 3 and Gd 2 O 3 was charged in a molibdenum crucible in a chamber, in which the atmospheric pressure was maintained at 10 -5 Torr and the crucible was heated by an induction coil to 1850 to 2000°C to melt the mixed powder in the crucible. Subsequently, unidirectional solidification was conducted by lowering the crucible, at a speed of 20 mm/hour and under the above atmospheric pressure, to obtain a unidirectionally solidified body.
  • Fig. 2 shows scanning electron micrograph of the thus obtained solidified body in a section cut perpendicular to the direction of the solidification.
  • the white portions are a GdAlO 3 phase and the black portions are an ⁇ -Al 2 O 3 phase.
  • the ceramic composite of the solidified body does not include any colony or grain boundary phase, that pores or voids do not exist, and that a uniform structure is obtained.
  • the mechanical strengths of the ceramic composite are shown in Tables 1 and 3, where the three point bending strength was measured at 1600°C in air with a strain speed of 10 -4 sec. The ceramic composite was kept at 1700°C for 50 hours and the increase in weight was 0.003 g/cm 3 .
  • Example 2 The procedures of Example 2 were repeated, except that the moving speed of the crucible was 50 mm/hour, to obtain a solidified body.
  • Figs. 3 and 4 show scanning electron micrographs of the solidified body in section cut perpendicular to and in parallel to the direction of the solidification. It is seen that this solidified body has a unique structure consisting of a structure which is finer than that of Example 2 and a structure wherein a GdAlO 3 phase in the form of fibers is uniformly dispersed in an Al 2 O 3 phase.
  • ⁇ -Al 2 O 3 powder and Gd 2 O 3 powder in the same molar ratio as in Example 1 were milled in a wet mill using ethanol.
  • the obtained slurry was dried in a rotary evaporator to remove the ethanol.
  • the obtained mixed powder of ⁇ -Al 2 O 3 and Gd 2 O 3 was charged in a graphite die and sintered, while being pressed at 500 kg/mm 2 in an atmospheric pressure of 10 -2 Torr, at a temperature of 1680°C for 2 hours to obtain a sintered body.
  • Fig. 5 shows scanning electron micrograph of the thus obtained sintered body in a section cut perpendicular to the direction of the pressing during sintering.
  • the white portions are GdAlO 3 grains and the black portions are ⁇ -Al 2 O 3 grains.
  • the sintered body was a ceramic composite comprising ⁇ -Al 2 O 3 grains and GdAlO 3 grains.
  • ⁇ -Al 2 O 3 powder and Er 2 O 3 powder in a molar ratio of 81.1% by mole of the former to 18.9% by mole of the latter were milled in a wet mill using ethanol.
  • the obtained slurry was dried in a rotary evaporator to remove the ethanol.
  • the obtained mixed powder of ⁇ -Al 2 O 3 and Er 2 O 3 was charged in a molibdenum crucible in a chamber, in which the atmospheric pressure was maintained at 10 -5 Torr, and the crucible was heated by an induction coil to 1900 to 2000°C to melt the mixed powder in the crucible. Subsequently, unidirectional solidification was conducted by lowering the crucible at a speed of 5 mm/hour, under the above atmospheric pressure, to obtain a unidirectionally solidified body.
  • Fig. 6 shows scanning electron micrograph of the thus obtained solidified body in a section cut perpendicular to the direction of the solidification.
  • the white portions are a Er 3 Al 5 O 12 phase and the black portions are an ⁇ -Al 2 O 3 phase.
  • the ceramic composite of the solidified body does not include any colony or grain boundary phase, that pores or voids do not exist, and that a uniform structure is obtained.
  • the mechanical strengths of the ceramic composite is shown in Tables 4 and 6, where the three point bending strength was measured at 1800°C in air and the compressive creep strength was measured at 1600°C in air with a strain speed of 10 -4 /sec. The ceramic composite was kept at 1700°C for 50 hours and the increase in weight was 0.002 g/cm 3 .
  • ⁇ -Al 2 O 3 powder and Er 2 O 3 powder in a molar ratio of 81.1% by mole of the former to 18.9% by mole of the latter were milled in a wet mill using ethanol.
  • the obtained slurry was dried in a rotary evaporator to remove the ethanol.
  • the obtained mixed powder of ⁇ -Al 2 O 3 and Er 2 O 3 was charged in a molibdenum crucible in a chamber, in which the atmospheric pressure was maintained at 10 -5 Torr and the crucible was heated by an induction coil to 1900 to 2000°C to melt the mixed powder in the crucible. Subsequently, unidirectional solidification was conducted by lowering the crucible at a speed of 50 mm/hour, under the above atmospheric pressure, to obtain a unidirectionally solidified body.
  • Fig. 7 shows scanning electron micrograph of the thus obtained solidified body in a section cut perpendicular to the direction of the solidification.
  • the white portions are a Er 3 Al 5 O 12 phase and the black portions are an ⁇ -Al 2 O 3 phase.
  • the ceramic composite of the solidified body does not include any colony or grain boundary phase, that pores or voids do not exist, and that a uniform structure is obtained.
  • the mechanical strengths of the ceramic composite is shown in Tables 5 and 6, where the three point bending strength was measured at 1800°C in air and the compressive creep strength was measured at 1600°C in air with a strain speed of 10 -4 /sec.
  • the ceramic composite was kept at 1700°C for 50 hours and the increase in weight was 0.002 g/cm 3 .
  • ⁇ -Al 2 O 3 powder and Er 2 O 3 powder in the same molar ratio as in Example 4 were milled in a wet mill using ethanol.
  • the obtained slurry was dried in a rotary evaporator to remove the ethanol.
  • the obtained mixed powder of ⁇ -Al 2 O 3 and Er 2 O 3 was charged in a graphite die and sintered, while being pressed at 500 kg/mm 2 at 1780°C, and an atmospheric pressure of 10 -2 Torr for 2 hours to obtain a sintered body.
  • X-ray diffraction of the thus obtained sintered body diffraction peaks from a plurality of planes of ⁇ -Al 2 O 3 and diffraction peaks from a plurality of planes of Er 3 Al 5 O 12 were observed.
  • Fig. 8 shows scanning electron micrograph of the sintered body in a section cut perpendicular to the direction of the pressing during the sintering.
  • the white portions are Er 3 Al 5 O 12 grains and the black portions are ⁇ -Al 2 O 3 grains.
  • the sintered body was a ceramic composite comprising ⁇ -Al 2 O 3 grains and Er 3 Al 5 O 12 grains.
  • ⁇ -Al 2 O 3 powder and Sm 2 O 3 powder in a molar ratio of 69.0% by mole of the former to 31.0% by mole of the latter were milled in a wet mill using ethanol.
  • the obtained slurry was dried in a rotary evaporator to remove the ethanol.
  • the obtained mixed powder of ⁇ -Al 2 O 3 and Sm 2 O 3 was charged in a molibdenum crucible in a chamber, in which the atmospheric pressure was maintained at 10 -5 Torr, and the crucible was heated by an induction coil to 1850 to 1950°C to melt the mixed powder in the crucible. Subsequently, unidirectional solidification was conducted by lowering the crucible at a speed of 50 mm/hour under the above atmospheric pressure to obtain a unidirectionally solidified body.
  • Fig. 9 shows scanning electron micrograph of the thus obtained solidified body in a section cut perpendicular to the direction of the solidification.
  • the white portions are a SmAlO 3 phase and the black portions are an ⁇ -Al 2 O 3 phase.
  • the ceramic composite of the solidified body does not include any colony or grain boundary phase, that pores or voids do not exist, and that a uniform structure is obtained.
  • the mechanical strengths of the ceramic composite is shown in Tables 7 and 8, where the three point bending strength was measured at 1700°C in air and the compressive creep strength was measured at 1600°C with a strain speed of 10 -4 /sec. The ceramic composite was kept at 1700°C for 50 hours and the increase in weight was 0.002 g/cm 3 .
  • Table 7 Example 6 Three point bending strength (MPa) 950 Table 8
  • ⁇ -Al 2 O 3 powder and Yb 2 O 3 powder in a molar ratio of 83.7% by mole of the former to 16.3% by mole of the latter were milled in a wet mill using ethanol.
  • the obtained slurry was dried in a rotary evaporator to remove ethanol.
  • the obtained mixed powder of ⁇ -Al 2 O 3 and Yb 2 O 3 was charged in a molibdenum crucible in a chamber, in which the atmospheric pressure was maintained at 10 -5 Torr, and the crucible was heated by an induction coil to 1850 to 1950°C to melt the mixed powder in the crucible. Subsequently, unidirectional solidification was conducted by lowering the crucible at a speed of 5 mm/hour under the above atmospheric pressure to obtain a unidirectionally solidified body.
  • Fig. 10 shows scanning electron micrograph of the thus obtained solidified body in a section cut perpendicular to the direction of the solidification.
  • the white portions are a 3Yb 2 O 3 ⁇ 5Al 2 O 3 phase and the black portions are an ⁇ -Al 2 O 3 phase.
  • the ceramic composite of the solidified body does not include any colony or grain boundary phase, pores or voids do not exist, and a uniform structure is obtained.
  • the mechanical strength of the ceramic composite is shown in Table 9, where the three point bending strength was measured at 1600°C in air. The ceramic composite was kept at 1700°C for 50 hours and the increase in weight was 0.002 g/cm 3 .
  • Table 9 Example 7 Three point bending strength (MPa) 550
  • the obtained mixed powder of ⁇ -Al 2 O 3 and La 2 O 3 was charged in a molibdenum crucible in a chamber, in which the atmospheric pressure was maintained at 10 -5 Torr and the crucible was heated by an induction coil to 1800 to 1900°C to melt the mixed powder in the crucible. Subsequently, unidirectional solidification was conducted by lowering the crucible at a speed of 50 mm/hour under the above atmospheric pressure to obtain a unidirectionally solidified body.
  • Fig. 11 shows scanning electron micrograph of the thus obtained solidified body in a section cut perpendicular to the direction of the solidification.
  • the white portions are an LaAlO 3 phase and the black portions are an ⁇ -Al 2 O 3 phase.
  • the ceramic composite of the solidified body does not include any colony or grain boundary phase, that pores or voids do not exist, and that a uniform structure is obtained.
  • the mechanical strength of the ceramic composite is shown in Table 10, where the three point bending strength was measured at 1600°C in air. The ceramic composite was kept at 1600°C for 50 hours and the increase in weight was 0.002 g/cm 3 .
  • Table 10 Example 8 Three point bending strength (MPa) 750
  • the obtained mixed powder of ⁇ -Al 2 O 3 and Nd 2 O 3 was charged in a molibdenum crucible in a chamber, in which the atmospheric pressure was maintained at 10 -5 Torr and the crucible was heated, by an induction coil, to 1850 to 1950°C to melt the mixed powder in the crucible. Subsequently, unidirectional solidification was conducted by lowering the crucible at a speed of 20 mm/hour, under the above atmospheric pressure, to obtain a unidirectionally solidified body.
  • Fig. 12 shows scanning electron micrograph of the thus obtained solidified body in a section cut perpendicular to the direction of the solidification.
  • the white portions are an NdAl 11 O 18 phase and the black portions are an AlNdO 3 phase.
  • the ceramic composite of the solidified body does not include any colony or grain boundary phase, that pores or voids do not exist, and that a uniform structure is obtained.
  • the mechanical strength of the ceramic composite is shown in Table 11, where the three point bending strength was measured at 1700°C in air.
  • the obtained mixed powder of ⁇ -Al 2 O 3 and Nd 2 O 3 was charged in a molibdenum crucible in a chamber, in which the atmospheric pressure was maintained at 10 -5 Torr, and the crucible was heated by an induction coil to 1850 to 1950°C to melt the mixed powder in the crucible. Subsequently, unidirectional solidification was conducted by lowering the crucible, at a speed of 50 mm/hour under the above atmospheric pressure, to obtain a unidirectionally solidified body.
  • Fig. 13 shows scanning electron micrograph of the thus obtained solidified body in a section cut perpendicular to the direction of the solidification.
  • the white portions are an NdAl 11 O 18 phase and the black portions are an AlNdO 3 phase.
  • the ceramic composite of the solidified body does not include any colony or grain boundary phase, that pores or voids do not exist, and that a uniform structure is obtained.
  • the mechanical strength of the ceramic composite is shown in Table 11, where the three point bending strength was measured at 1700°C in air.
  • Table 11 Example 9
  • the obtained mixed powder of ⁇ -Al 2 O 3 and Eu 2 O 3 was charged in a molibdenum crucible in a chamber, in which the atmospheric pressure was maintained at 10 -5 Torr, and the crucible was heated by an induction coil to 1750 to 1850°C to melt the mixed powder in the crucible. Subsequently, unidirectional solidification was conducted by lowering the crucible at a speed of 20 mm/hour under the above atmospheric pressure to obtain a unidirectionally solidified body.
  • Fig. 14 shows scanning electron micrograph of the thus obtained solidified body in a section cut perpendicular to the direction of the solidification.
  • the white portions are an AlEuO 3 phase and the black portions are an EuAl 11 O 18 phase.
  • the ceramic composite of the solidified body does not include any colony or grain boundary phase, that pores or voids do not exist, and that a uniform structure is obtained.
  • the mechanical strength of the ceramic composite is shown in Table 12, where the three point bending strength was measured at 1600°C in air.
  • the obtained mixed powder of ⁇ -Al 2 O 3 and Pr 6 O 11 was charged in a molibdenum crucible in a chamber, in which the atmospheric pressure was maintained at 10 -5 Torr, and the crucible was heated by an induction coil to 1900 to 1950°C to melt the mixed powder in the crucible. Subsequently, unidirectional solidification was conducted by lowering the crucible at a speed of 20 mm/hour under the above atmospheric pressure to obtain a unidirectionally solidified body.
  • Fig. 15 shows scanning electron micrograph of the thus obtained solidified body in a section cut perpendicular to the direction of the solidification.
  • the white portions are a PrAlO 3 phase and the black portions are a PrAl 11 O 18 phase, both phases being a complex metal oxide.
  • the ceramic composite of the solidified body does not include any colony or grain boundary phase, that pores or voids do not exist, and that a uniform structure is obtained.
  • the mechanical strength of the ceramic composite is shown in Table 12, where the three point bending strength was measured at 1600°C in air.
  • Table 12 Example 1
  • ⁇ -Al 2 O 3 powder and SiO 2 powder in a molar ratio of 68.0% by mole of the former to 32.0% by mole of the latter were milled in a wet mill using ethanol.
  • the obtained slurry was dried in a rotary evaporator to remove the ethanol.
  • the obtained mixed powder of ⁇ -Al 2 O 3 and SiO 2 was charged in a molibdenum crucible in a chamber, in which the atmospheric pressure was maintained at 10 -2 Torr, and the crucible was heated by an induction coil to 1950 to 2100°C to melt the mixed powder in the crucible. Subsequently, unidirectional solidification was conducted by lowering the crucible at a speed of 5 mm/hour under the above atmospheric pressure to obtain a unidirectionally solidified body.
  • Fig. 16 shows scanning electron micrograph of the thus obtained solidified body in a section cut perpendicular to the direction of the solidification.
  • the white portions are a 3Al 2 O 3 ⁇ 2SiO 2 (mullite) phase and the dark portions are an ⁇ -Al 2 O 3 phase.
  • the ceramic composite of the solidified body does not include any colony or grain boundary phase, that pores or voids do not exist, and that a uniform structure is obtained.
  • the mechanical strength of the ceramic composite is shown in Table 13, where the three point bending strength was measured at 1850°C in argon. The ceramic composite was kept at 1700°C for 50 hours and the increase in weight was 0.003 g/cm 3 .
  • Example 13 The procecures of Example 13 were repeated except that the pressure in the chamber was changed to normal pressure (atmospheric pressure).
  • Fig. 17 shows scanning electron micrograph of the thus obtained solidified body consisting of ⁇ -Al 2 O 3 and 3Al 2 O 3 ⁇ 2SiO 2 in a section cut perpendicular to the direction of the solidification. It was demonstrated that the ceramic composite of the solidified body included colonies and grain boundary phases as well as pores.
  • the obtained mixed powder of ⁇ -Al 2 O 3 and SiO 2 was charged in a molibdenum crucible in a chamber, in which the atmospheric pressure was maintained at 10 -2 Torr and the crucible was heated by an induction coil to 1950 to 2100°C to melt the mixed powder in the crucible. Subsequently, unidirectional solidification was conducted by lowering the crucible at a speed of 60 mm/hour under the above atmospheric pressure to obtain a unidirectionally solidified body.
  • Fig. 18 shows scanning electron micrograph of the thus obtained solidified body in a section cut perpendicular to the direction of the solidification.
  • the white portions are a 3Al 2 O 3 ⁇ 2Al 2 O 3 (mullite) phase and the dark portions are an ⁇ -Al 2 O 3 phase.
  • the ceramic composite of the solidified body does not include any colony or grain boundary phase, that pores or voids do not exist, and that a uniform structure is obtained.
  • the mechanical strength of the ceramic composite is shown in Table 13, where the three point bending strength was measured at 1700°C in argon. The ceramic composite was kept at 1700°C for 50 hours and the increase in weight was 0.003 g/cm 3 .
  • Example 14 The procedures of Example 14 were repeated except that the pressure in the chamber was changed to normal pressure (atmospheric pressure).
  • Fig. 19 shows scanning electron micrograph of the thus obtained solidified body consisting of ⁇ -Al 2 O 3 and 3Al 2 O 3 ⁇ 2SiO 2 in a section cut perpendicular to the direction of the solidification. It was demonstrated that the ceramic composite of the solidified body included colonies and grain boundary phases as well as pores.
  • ⁇ -Al 2 O 3 powder and SiO 2 powder in a molar ratio of 68.0% by mole of the former to 32.0% by mole of the latter were milled in a wet mill using ethanol.
  • the obtained slurry was dried in a rotary evaporator to remove the ethanol.
  • the obtained mixed powder of ⁇ -Al 2 O 3 and SiO 2 was charged in a molibdenum crucible in a chamber, in which the atmospheric pressure was maintained at 10 -2 Torr, and the crucible was heated by an induction coil to 1950 to 2100°C to melt the mixed powder in the crucible. Subsequently, unidirectional solidification was conducted by lowering the crucible at a speed of 220 mm/hour under the above atmospheric pressure to obtain a unidirectionally solidified body.
  • Fig. 20 shows scanning electron micrograph of the thus obtained solidified body in a section cut perpendicular to the direction of the solidification.
  • the white portions are a 3Al 2 O 3 ⁇ 2SiO 2 (mullite) phase and the dark portions are an ⁇ -Al 2 O 3 phase.
  • the ceramic composite of the solidified body does not include any colony or grain boundary phase, that pores or voids do not exist, and that a uniform structure is obtained.
  • the mechanical strength of the ceramic composite is shown in Table 17, where the three point bending strength was measured at 1850°C in argon. The ceramic composite was kept at 1700°C for 50 hours and the increase in weight was 0.003 g/cm 3 .
  • Table 17 Example 13
  • Example 14 Example 15 Three point bending strength (MPa) 400 450 550
  • Example 15 The procedures of Example 15 were repeated except that the pressure in the chamber was changed to normal pressure (atmospheric pressure).
  • Fig. 21 shows scanning electron micrograph of the thus obtained solidified body consisting of ⁇ -Al 2 O 3 and 3Al 2 O 3 ⁇ 2SiO 2 in a section cut perpendicular to the direction of the solidification. It was demonstrated that the ceramic composite of the solidified body included colonies and grain boundary phases as well as pores.
  • ⁇ -Al 2 O 3 powder and ZrO 2 powder in a molar ratio of 50.4% by mole of the former to 49.6% by mole of the latter were milled in a wet mill using ethanol.
  • the obtained slurry was dried in a rotary evaporator to remove the ethanol.
  • the obtained mixed powder of ⁇ -Al 2 O 3 and ZrO 2 was charged in a molibdenum crucible in a chamber, in which the atmospheric pressure was maintained at 10 -5 Torr and the crucible was heated by an induction coil to 1950 to 2100°C to melt the mixed powder in the crucible. Subsequently, unidirectional solidification was conducted by lowering the crucible at a speed of 5 mm/hour under the above atmospheric pressure to obtain a unidirectionally solidified body.
  • Fig. 22 shows scanning electron micrograph of the thus obtained solidified body in a section cut perpendicular to the direction of the solidification.
  • the white portions are a ZrO 2 phase and the black portions are an ⁇ -Al 2 O 3 phase.
  • the ceramic composite of the solidified body does not include any colonies or grain boundary phases, that pores or voids do not exist, and that a uniform structure is obtained.
  • the mechanical strength of the ceramic composite is shown in Table 19, where the three point bending strength was measured at 1600°C in argon. The ceramic composite was kept at 1700°C for 50 hours and the increase in weight was 0.003 g/cm 3 . Further, the fracture toughness of the ceramic composite was measured, at room temperature and by the IF method, to be a high value of 10 MPa ⁇ m Table 19

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Compositions Of Oxide Ceramics (AREA)
EP96100600A 1995-01-19 1996-01-17 Keramischer Verbundkörper Expired - Lifetime EP0722919B1 (de)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
JP23286/95 1995-01-19
JP2328795 1995-01-19
JP2328695 1995-01-19
JP2328895 1995-01-19
JP23287/95 1995-01-19
JP2328695 1995-01-19
JP2328795 1995-01-19
JP2328895 1995-01-19
JP23288/95 1995-01-19
JP17798595 1995-06-22
JP17798595 1995-06-22
JP177985/95 1995-06-22

Publications (2)

Publication Number Publication Date
EP0722919A1 true EP0722919A1 (de) 1996-07-24
EP0722919B1 EP0722919B1 (de) 1999-08-11

Family

ID=27457927

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96100600A Expired - Lifetime EP0722919B1 (de) 1995-01-19 1996-01-17 Keramischer Verbundkörper

Country Status (4)

Country Link
US (1) US5902763A (de)
EP (1) EP0722919B1 (de)
CN (1) CN1064937C (de)
DE (1) DE69603627T2 (de)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0914883A1 (de) * 1997-10-30 1999-05-12 Howmet Research Corporation Formkern mit Erbiumoxid
WO2001056948A1 (en) * 2000-02-02 2001-08-09 3M Innovative Properties Company FUSED A1203-Mg0-RARE EARTH OXIDE EUTECTIC ABRASIVE PARTICLES, ABRASIVE ARTICLES, AND METHODS OF MAKING AND USING THE SAME
WO2001056946A1 (en) * 2000-02-02 2001-08-09 3M Innovative Properties Company FUSED Al2O3-RARE EARTH OXIDE EUTECTIC ABRASIVE PARTICLES, ABRASIVE ARTICLES, AND METHODS OF MAKING AND USING THE SAME
WO2001056950A1 (en) * 2000-02-02 2001-08-09 3M Innovative Properties Company Fused abrasive particles, abrasive articles, and methods of making and using the same
WO2002008145A1 (en) * 2000-07-19 2002-01-31 3M Innovative Properties Company FUSED ALUMINUM OXYCARBIDE/NITRIDE-Al2O3. RARE EARTH OXIDE EUTECTIC MATERIALS, ABRASIVE PARTICLES, ABRASIVE ARTICLES, AND METHODS OF MAKING AND USING THE SAME
WO2002008146A1 (en) * 2000-07-19 2002-01-31 3M Innovative Properties Company Fused al2o3-rare earth oxide-zro2 eutectic materials, abrasive particles, abrasive articles, and methods of making and using the same
EP1279650A1 (de) * 2001-07-23 2003-01-29 NGK Spark Plug Company Limited Gesintertes Aluminiumoxid Keramik, Verfahren zur Herstellung desselben, und ein Schneidewerkzeug
US6749653B2 (en) 2002-02-21 2004-06-15 3M Innovative Properties Company Abrasive particles containing sintered, polycrystalline zirconia
US6984261B2 (en) 2003-02-05 2006-01-10 3M Innovative Properties Company Use of ceramics in dental and orthodontic applications
US7101819B2 (en) 2001-08-02 2006-09-05 3M Innovative Properties Company Alumina-zirconia, and methods of making and using the same
US7141523B2 (en) 2003-09-18 2006-11-28 3M Innovative Properties Company Ceramics comprising Al2O3, REO, ZrO2 and/or HfO2, and Nb2O5 and/or Ta2O5 and methods of making the same
US7141522B2 (en) 2003-09-18 2006-11-28 3M Innovative Properties Company Ceramics comprising Al2O3, Y2O3, ZrO2 and/or HfO2, and Nb2O5 and/or Ta2O5 and methods of making the same
US7175786B2 (en) 2003-02-05 2007-02-13 3M Innovative Properties Co. Methods of making Al2O3-SiO2 ceramics
US7179526B2 (en) 2002-08-02 2007-02-20 3M Innovative Properties Company Plasma spraying
US7197896B2 (en) 2003-09-05 2007-04-03 3M Innovative Properties Company Methods of making Al2O3-SiO2 ceramics
US7258707B2 (en) 2003-02-05 2007-08-21 3M Innovative Properties Company AI2O3-La2O3-Y2O3-MgO ceramics, and methods of making the same
US7292766B2 (en) 2003-04-28 2007-11-06 3M Innovative Properties Company Use of glasses containing rare earth oxide, alumina, and zirconia and dopant in optical waveguides
US7297171B2 (en) 2003-09-18 2007-11-20 3M Innovative Properties Company Methods of making ceramics comprising Al2O3, REO, ZrO2 and/or HfO2 and Nb205 and/or Ta2O5
US7384438B1 (en) 2000-07-19 2008-06-10 3M Innovative Properties Company Fused Al2O3-Y2O3-ZrO2 eutectic abrasive particles, abrasive articles, and methods of making and using the same
US7507268B2 (en) 2001-08-02 2009-03-24 3M Innovative Properties Company Al2O3-Y2O3-ZrO2/HfO2 materials, and methods of making and using the same
US7563293B2 (en) 2001-08-02 2009-07-21 3M Innovative Properties Company Al2O3-rare earth oxide-ZrO2/HfO2 materials, and methods of making and using the same
US7563294B2 (en) 2001-08-02 2009-07-21 3M Innovative Properties Company Abrasive particles and methods of making and using the same
US7625509B2 (en) 2001-08-02 2009-12-01 3M Innovative Properties Company Method of making ceramic articles
US7662735B2 (en) 2002-08-02 2010-02-16 3M Innovative Properties Company Ceramic fibers and composites comprising same
US7811496B2 (en) 2003-02-05 2010-10-12 3M Innovative Properties Company Methods of making ceramic particles
US8003217B2 (en) 2001-08-02 2011-08-23 3M Innovative Properties Company Metal oxide ceramic and method of making articles therewith

Families Citing this family (63)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6383964B1 (en) * 1998-11-27 2002-05-07 Kyocera Corporation Ceramic member resistant to halogen-plasma corrosion
DE69920152T2 (de) * 1998-12-21 2005-09-22 Shin-Etsu Chemical Co., Ltd. Korrosionbeständiges Mischoxidmaterial
KR20010062209A (ko) * 1999-12-10 2001-07-07 히가시 데쓰로 고내식성 막이 내부에 형성된 챔버를 구비하는 처리 장치
US6451077B1 (en) 2000-02-02 2002-09-17 3M Innovative Properties Company Fused abrasive particles, abrasive articles, and methods of making and using the same
US6669749B1 (en) 2000-02-02 2003-12-30 3M Innovative Properties Company Fused abrasive particles, abrasive articles, and methods of making and using the same
US6592640B1 (en) 2000-02-02 2003-07-15 3M Innovative Properties Company Fused Al2O3-Y2O3 eutectic abrasive particles, abrasive articles, and methods of making and using the same
US6410471B2 (en) * 2000-03-07 2002-06-25 Shin-Etsu Chemical Co., Ltd. Method for preparation of sintered body of rare earth oxide
US6583080B1 (en) 2000-07-19 2003-06-24 3M Innovative Properties Company Fused aluminum oxycarbide/nitride-Al2O3·rare earth oxide eutectic materials
US6458731B1 (en) 2000-07-19 2002-10-01 3M Innovative Properties Company Fused aluminum oxycarbide/nitride-AL2O3.Y2O3 eutectic materials
US6454822B1 (en) 2000-07-19 2002-09-24 3M Innovative Properties Company Fused aluminum oxycarbide/nitride-Al2O3·Y2O3 eutectic abrasive particles, abrasive articles, and methods of making and using the same
US6582488B1 (en) 2000-07-19 2003-06-24 3M Innovative Properties Company Fused Al2O3-rare earth oxide-ZrO2 eutectic materials
US6589305B1 (en) 2000-07-19 2003-07-08 3M Innovative Properties Company Fused aluminum oxycarbide/nitride-Al2O3 • rare earth oxide eutectic abrasive particles, abrasive articles, and methods of making and using the same
US6666750B1 (en) 2000-07-19 2003-12-23 3M Innovative Properties Company Fused AL2O3-rare earth oxide-ZrO2 eutectic abrasive particles, abrasive articles, and methods of making and using the same
US6620756B2 (en) * 2001-06-20 2003-09-16 Ues, Inc. Ceramic matrix composite cutting tool material
US20080264564A1 (en) * 2007-04-27 2008-10-30 Applied Materials, Inc. Method of reducing the erosion rate of semiconductor processing apparatus exposed to halogen-containing plasmas
US20080213496A1 (en) * 2002-02-14 2008-09-04 Applied Materials, Inc. Method of coating semiconductor processing apparatus with protective yttrium-containing coatings
US6789498B2 (en) 2002-02-27 2004-09-14 Applied Materials, Inc. Elements having erosion resistance
US6837966B2 (en) * 2002-09-30 2005-01-04 Tokyo Electron Limeted Method and apparatus for an improved baffle plate in a plasma processing system
US6798519B2 (en) 2002-09-30 2004-09-28 Tokyo Electron Limited Method and apparatus for an improved optical window deposition shield in a plasma processing system
US7147749B2 (en) * 2002-09-30 2006-12-12 Tokyo Electron Limited Method and apparatus for an improved upper electrode plate with deposition shield in a plasma processing system
US7204912B2 (en) * 2002-09-30 2007-04-17 Tokyo Electron Limited Method and apparatus for an improved bellows shield in a plasma processing system
US7137353B2 (en) * 2002-09-30 2006-11-21 Tokyo Electron Limited Method and apparatus for an improved deposition shield in a plasma processing system
US7166166B2 (en) * 2002-09-30 2007-01-23 Tokyo Electron Limited Method and apparatus for an improved baffle plate in a plasma processing system
US7166200B2 (en) * 2002-09-30 2007-01-23 Tokyo Electron Limited Method and apparatus for an improved upper electrode plate in a plasma processing system
KR100772740B1 (ko) 2002-11-28 2007-11-01 동경 엘렉트론 주식회사 플라즈마 처리 용기 내부재
CN1738781A (zh) 2003-01-20 2006-02-22 宇部兴产株式会社 用于光转化的陶瓷复合材料及其应用
US20040148869A1 (en) * 2003-02-05 2004-08-05 3M Innovative Properties Company Ceramics and methods of making the same
US7291566B2 (en) * 2003-03-31 2007-11-06 Tokyo Electron Limited Barrier layer for a processing element and a method of forming the same
US7560376B2 (en) 2003-03-31 2009-07-14 Tokyo Electron Limited Method for adjoining adjacent coatings on a processing element
US20050132656A1 (en) * 2003-12-18 2005-06-23 3M Innovative Properties Company Method of making abrasive particles
US20050137077A1 (en) * 2003-12-18 2005-06-23 3M Innovative Properties Company Method of making abrasive particles
EP1760794B1 (de) * 2004-06-24 2014-01-15 Ube Industries, Ltd. Weisslicht emittierende leuchtdiodenvorrichtung
US7497093B2 (en) * 2004-07-29 2009-03-03 3M Innovative Properties Company Method of making ceramic articles
US7332453B2 (en) * 2004-07-29 2008-02-19 3M Innovative Properties Company Ceramics, and methods of making and using the same
US7552521B2 (en) * 2004-12-08 2009-06-30 Tokyo Electron Limited Method and apparatus for improved baffle plate
KR100885694B1 (ko) * 2004-12-17 2009-02-26 우베 고산 가부시키가이샤 광변환 구조체 및 그것을 이용한 발광장치
US7601242B2 (en) * 2005-01-11 2009-10-13 Tokyo Electron Limited Plasma processing system and baffle assembly for use in plasma processing system
US20060225654A1 (en) * 2005-03-29 2006-10-12 Fink Steven T Disposable plasma reactor materials and methods
KR101036530B1 (ko) * 2005-08-10 2011-05-24 우베 고산 가부시키가이샤 발광 다이오드용 기판 및 발광 다이오드
DE102005043398A1 (de) * 2005-09-08 2007-03-15 Forschungsverbund Berlin E.V. Verfahren zur Herstellung eines Titan-Saphir-Laserkristalls
US7281970B2 (en) 2005-12-30 2007-10-16 3M Innovative Properties Company Composite articles and methods of making the same
US7598188B2 (en) 2005-12-30 2009-10-06 3M Innovative Properties Company Ceramic materials and methods of making and using the same
CN101370908B (zh) * 2006-01-19 2012-04-18 宇部兴产株式会社 陶瓷复合体光转换构件和用其的发光装置
US8093799B2 (en) * 2006-09-25 2012-01-10 Ube Industries, Ltd. Ceramic composite for phototransformation and light emitting device using the same
US7696117B2 (en) * 2007-04-27 2010-04-13 Applied Materials, Inc. Method and apparatus which reduce the erosion rate of surfaces exposed to halogen-containing plasmas
US10242888B2 (en) 2007-04-27 2019-03-26 Applied Materials, Inc. Semiconductor processing apparatus with a ceramic-comprising surface which exhibits fracture toughness and halogen plasma resistance
US10622194B2 (en) 2007-04-27 2020-04-14 Applied Materials, Inc. Bulk sintered solid solution ceramic which exhibits fracture toughness and halogen plasma resistance
US8367227B2 (en) * 2007-08-02 2013-02-05 Applied Materials, Inc. Plasma-resistant ceramics with controlled electrical resistivity
CN101182212B (zh) * 2007-11-06 2010-04-07 武汉理工大学 硼化物-氧化物复相陶瓷及其制备方法
MX2010005354A (es) * 2007-11-15 2010-09-03 Univ Rutgers Metodo de sinterizacion en fase liquida hidrotermica de materiales ceramicos y productos derivados del mismo.
US20110021340A1 (en) * 2009-07-24 2011-01-27 Karl-Heinz Schofalvi Refractory
JP5621131B2 (ja) * 2010-03-10 2014-11-05 シチズンファインテックミヨタ株式会社 高絶縁、高安定性圧電ｌｔｇａ単結晶及びその製造方法、並びにそのｌｔｇａ単結晶を使用する圧電素子及び燃焼圧センサー
JP5712768B2 (ja) * 2010-05-10 2015-05-07 信越化学工業株式会社 波長変換部材、発光装置、及び波長変換部材の製造方法
US9988309B2 (en) * 2012-05-20 2018-06-05 Skyworks Solutions, Inc. Thermal barrier coating material with enhanced toughness
US10501373B1 (en) * 2014-01-24 2019-12-10 United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration Multi-phase ceramic system
JP6420697B2 (ja) * 2014-03-19 2018-11-07 日本碍子株式会社 複合体、ハニカム構造体及び複合体の製造方法
CN104751903B (zh) * 2015-03-11 2017-07-18 中国核动力研究设计院 一种TiO2掺杂UO2‑10wt%Gd2O3可燃毒物及其制备方法
US10246375B2 (en) 2016-03-30 2019-04-02 Skyworks Solutions, Inc. Multi-phase high thermal conductivity composite dielectric materials
FR3052773B1 (fr) * 2016-06-15 2020-10-30 Snecma Procede de fabrication d'une piece de turbomachine
CN110294628A (zh) * 2018-03-21 2019-10-01 深圳光峰科技股份有限公司 发光陶瓷及其制备方法
TWI849367B (zh) 2020-12-28 2024-07-21 財團法人工業技術研究院 陶瓷材料與銲線瓷嘴
US12512232B2 (en) 2020-12-29 2025-12-30 Skyworks Solutions, Inc. Low loss tangent dielectric based on spinel-structured oxide
CN115121785B (zh) * 2022-07-06 2023-02-14 青岛正望新材料股份有限公司 一种炼钢用功能性耐火材料

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3653432A (en) * 1970-09-01 1972-04-04 Us Army Apparatus and method for unidirectionally solidifying high temperature material
US4829028A (en) * 1985-10-25 1989-05-09 The Japan Carlit Co., Ltd. Process for producing an alumina-zirconia composite sintered material
EP0374263A1 (de) * 1988-06-06 1990-06-27 Nippon Steel Corporation Supraleitendes oxidmaterial und verfahren zur herstellung
EP0647601A1 (de) * 1993-10-08 1995-04-12 Ube Industries, Ltd. Keramischer Verbundwerkstoff
EP0654456A1 (de) * 1993-11-12 1995-05-24 Ube Industries, Ltd. Keramischer Verbundwerkstoff

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4316964A (en) * 1980-07-14 1982-02-23 Rockwell International Corporation Al2 O3 /ZrO2 ceramic
US5208193A (en) * 1982-12-20 1993-05-04 The Dow Chemical Company Ceramic composites with improved thermal shock resistance
US5028572A (en) * 1986-02-04 1991-07-02 The Carborundum Company Near net shape fused cast refractories and process for their manufacture by rapid melting/controlled rapid cooling
JPS63117952A (ja) * 1986-11-07 1988-05-21 呉羽化学工業株式会社 高靭性コランダム−ルチル複合焼結体およびその製造方法
US4837187A (en) * 1987-06-04 1989-06-06 Howmet Corporation Alumina-based core containing yttria
JPH01119559A (ja) * 1987-11-02 1989-05-11 Kureha Chem Ind Co Ltd ムライト−アルミナ複合焼結体及びその製造方法
US5278137A (en) * 1988-06-06 1994-01-11 Nippon Steel Corporation YBa2 Cu3 O7-y type oxide superconductive material containing dispersed Y2 BaCuO5 phase and having high critical current density
JP2926966B2 (ja) * 1989-11-28 1999-07-28 旭硝子株式会社 高ジルコニア質熱溶融鋳造耐火物
JP3007730B2 (ja) * 1991-09-26 2000-02-07 守 大森 希土類酸化物−アルミナ焼結体およびその製造方法
US5175132A (en) * 1991-11-19 1992-12-29 Ketcham Thomas D Sinterable ceramic compositions
JPH0715095B2 (ja) * 1992-10-23 1995-02-22 日本研磨材工業株式会社 セラミック砥粒及びその製造方法並びに研磨製品
CA2102656A1 (en) * 1992-12-14 1994-06-15 Dwight D. Erickson Abrasive grain comprising calcium oxide and/or strontium oxide
JP3264106B2 (ja) * 1993-11-12 2002-03-11 宇部興産株式会社 セラミックス複合材料

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3653432A (en) * 1970-09-01 1972-04-04 Us Army Apparatus and method for unidirectionally solidifying high temperature material
US4829028A (en) * 1985-10-25 1989-05-09 The Japan Carlit Co., Ltd. Process for producing an alumina-zirconia composite sintered material
EP0374263A1 (de) * 1988-06-06 1990-06-27 Nippon Steel Corporation Supraleitendes oxidmaterial und verfahren zur herstellung
EP0647601A1 (de) * 1993-10-08 1995-04-12 Ube Industries, Ltd. Keramischer Verbundwerkstoff
EP0654456A1 (de) * 1993-11-12 1995-05-24 Ube Industries, Ltd. Keramischer Verbundwerkstoff

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
T.A. PARTHASARATHY ET AL., J. AMER. CERAM. SOC., vol. 76, no. 1, 1993, pages 29 - 32, XP002002491 *

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5977007A (en) * 1997-10-30 1999-11-02 Howmet Research Corporation Erbia-bearing core
EP0914883A1 (de) * 1997-10-30 1999-05-12 Howmet Research Corporation Formkern mit Erbiumoxid
WO2001056948A1 (en) * 2000-02-02 2001-08-09 3M Innovative Properties Company FUSED A1203-Mg0-RARE EARTH OXIDE EUTECTIC ABRASIVE PARTICLES, ABRASIVE ARTICLES, AND METHODS OF MAKING AND USING THE SAME
WO2001056946A1 (en) * 2000-02-02 2001-08-09 3M Innovative Properties Company FUSED Al2O3-RARE EARTH OXIDE EUTECTIC ABRASIVE PARTICLES, ABRASIVE ARTICLES, AND METHODS OF MAKING AND USING THE SAME
WO2001056950A1 (en) * 2000-02-02 2001-08-09 3M Innovative Properties Company Fused abrasive particles, abrasive articles, and methods of making and using the same
US7384438B1 (en) 2000-07-19 2008-06-10 3M Innovative Properties Company Fused Al2O3-Y2O3-ZrO2 eutectic abrasive particles, abrasive articles, and methods of making and using the same
WO2002008145A1 (en) * 2000-07-19 2002-01-31 3M Innovative Properties Company FUSED ALUMINUM OXYCARBIDE/NITRIDE-Al2O3. RARE EARTH OXIDE EUTECTIC MATERIALS, ABRASIVE PARTICLES, ABRASIVE ARTICLES, AND METHODS OF MAKING AND USING THE SAME
WO2002008146A1 (en) * 2000-07-19 2002-01-31 3M Innovative Properties Company Fused al2o3-rare earth oxide-zro2 eutectic materials, abrasive particles, abrasive articles, and methods of making and using the same
EP1279650A1 (de) * 2001-07-23 2003-01-29 NGK Spark Plug Company Limited Gesintertes Aluminiumoxid Keramik, Verfahren zur Herstellung desselben, und ein Schneidewerkzeug
US6753284B2 (en) 2001-07-23 2004-06-22 Ngk Spark Plug Co., Ltd. Sintered alumina ceramic, method for producing the same, and cutting tool
US7501000B2 (en) 2001-08-02 2009-03-10 3M Innovative Properties Company Abrasive particles, abrasive articles, and methods of making and using the same
US7737063B2 (en) 2001-08-02 2010-06-15 3M Innovative Properties Company AI2O3-rare earth oxide-ZrO2/HfO2 materials, and methods of making and using the same
US7101819B2 (en) 2001-08-02 2006-09-05 3M Innovative Properties Company Alumina-zirconia, and methods of making and using the same
US7507268B2 (en) 2001-08-02 2009-03-24 3M Innovative Properties Company Al2O3-Y2O3-ZrO2/HfO2 materials, and methods of making and using the same
US8003217B2 (en) 2001-08-02 2011-08-23 3M Innovative Properties Company Metal oxide ceramic and method of making articles therewith
US7147544B2 (en) 2001-08-02 2006-12-12 3M Innovative Properties Company Glass-ceramics
US7168267B2 (en) 2001-08-02 2007-01-30 3M Innovative Properties Company Method of making amorphous materials and ceramics
US7501001B2 (en) 2001-08-02 2009-03-10 3M Innovative Properties Company Abrasive particles, and methods of making and using the same
US7510585B2 (en) 2001-08-02 2009-03-31 3M Innovative Properties Company Ceramic materials, abrasive particles, abrasive articles, and methods of making and using the same
US7563293B2 (en) 2001-08-02 2009-07-21 3M Innovative Properties Company Al2O3-rare earth oxide-ZrO2/HfO2 materials, and methods of making and using the same
US7625509B2 (en) 2001-08-02 2009-12-01 3M Innovative Properties Company Method of making ceramic articles
US7563294B2 (en) 2001-08-02 2009-07-21 3M Innovative Properties Company Abrasive particles and methods of making and using the same
US6749653B2 (en) 2002-02-21 2004-06-15 3M Innovative Properties Company Abrasive particles containing sintered, polycrystalline zirconia
US7662735B2 (en) 2002-08-02 2010-02-16 3M Innovative Properties Company Ceramic fibers and composites comprising same
US7179526B2 (en) 2002-08-02 2007-02-20 3M Innovative Properties Company Plasma spraying
US8056370B2 (en) 2002-08-02 2011-11-15 3M Innovative Properties Company Method of making amorphous and ceramics via melt spinning
US7175786B2 (en) 2003-02-05 2007-02-13 3M Innovative Properties Co. Methods of making Al2O3-SiO2 ceramics
US6984261B2 (en) 2003-02-05 2006-01-10 3M Innovative Properties Company Use of ceramics in dental and orthodontic applications
US7258707B2 (en) 2003-02-05 2007-08-21 3M Innovative Properties Company AI2O3-La2O3-Y2O3-MgO ceramics, and methods of making the same
US7022173B2 (en) 2003-02-05 2006-04-04 3M Innovative Properties Company Use of ceramics in dental and orthodontic applications
US7811496B2 (en) 2003-02-05 2010-10-12 3M Innovative Properties Company Methods of making ceramic particles
US7292766B2 (en) 2003-04-28 2007-11-06 3M Innovative Properties Company Use of glasses containing rare earth oxide, alumina, and zirconia and dopant in optical waveguides
US7197896B2 (en) 2003-09-05 2007-04-03 3M Innovative Properties Company Methods of making Al2O3-SiO2 ceramics
US7297646B2 (en) 2003-09-18 2007-11-20 3M Innovative Properties Company Ceramics comprising Al2O3, REO, ZrO2 and/or HfO2, and Nb2O5 and/or Ta2O5 and methods of making the same
US7297171B2 (en) 2003-09-18 2007-11-20 3M Innovative Properties Company Methods of making ceramics comprising Al2O3, REO, ZrO2 and/or HfO2 and Nb205 and/or Ta2O5
US7253128B2 (en) 2003-09-18 2007-08-07 3M Innovative Properties Company Ceramics comprising AI2O3, Y2O3, ZrO2 and/or HfO2, and Nb2O5 and/or Ta2O5 and methods of making the same
US7141522B2 (en) 2003-09-18 2006-11-28 3M Innovative Properties Company Ceramics comprising Al2O3, Y2O3, ZrO2 and/or HfO2, and Nb2O5 and/or Ta2O5 and methods of making the same
US7141523B2 (en) 2003-09-18 2006-11-28 3M Innovative Properties Company Ceramics comprising Al2O3, REO, ZrO2 and/or HfO2, and Nb2O5 and/or Ta2O5 and methods of making the same

Also Published As

Publication number Publication date
DE69603627D1 (de) 1999-09-16
DE69603627T2 (de) 1999-12-30
EP0722919B1 (de) 1999-08-11
US5902763A (en) 1999-05-11
CN1140155A (zh) 1997-01-15
CN1064937C (zh) 2001-04-25

Similar Documents

Publication Publication Date Title
US5902763A (en) Fused ceramic composite
US5981415A (en) Ceramic composite material and porous ceramic material
EP0647601B1 (de) Keramischer Verbundwerkstoff
EP0654456B1 (de) Keramischer Verbundwerkstoff
US4851375A (en) Methods of making composite ceramic articles having embedded filler
US5298470A (en) Silicon carbide bodies having high toughness and fracture resistance and method of making same
US4719187A (en) Dense sintered bodies of nitride materials
Carry et al. Structural superplasticity in single phase crystalline ceramics
US5334562A (en) Composite ceramic articles
JP3743462B2 (ja) セラミックス複合材料
JPH03237060A (ja) 高靭性のセラミック合金
US5384293A (en) Rare earth oxide-alumina-silica sintered body and method of producing the same
JP3412381B2 (ja) セラミックス複合材料
Wang et al. Nucleation and growth of silicon oxynitride grains in a fine‐grained silicon nitride matrix
EP0495677B1 (de) Supraleitendes Oxidmaterial und Verfahren zu seiner Herstellung
JP3412378B2 (ja) セラミックス複合材料
US5439853A (en) Mixed oxide composite ceramics and method of producing the same
JP3007730B2 (ja) 希土類酸化物−アルミナ焼結体およびその製造方法
JPH08253390A (ja) セラミックス複合材料
US4331771A (en) High density silicon oxynitride
US4550063A (en) Silicon nitride reinforced nickel alloy composite materials
EP0963360A1 (de) Gasdruckgesintertes siliciumnitrid mit hoher festigkeit und bruchspannungsbeständigkeit
JPH0375508B2 (de)
JP3405083B2 (ja) 多孔質セラミックス材料
JP3148559B2 (ja) セラミックス繊維強化タービン翼及びその製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB

17P Request for examination filed

Effective date: 19961031

17Q First examination report despatched

Effective date: 19980403

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 69603627

Country of ref document: DE

Date of ref document: 19990916

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20150113

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20150114

Year of fee payment: 20

Ref country code: FR

Payment date: 20150108

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 69603627

Country of ref document: DE

Representative=s name: HOEGER, STELLRECHT & PARTNER PATENTANWAELTE MB, DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69603627

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20160116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20160116